JPH0812401B2 - Photographic support - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention relates to a photographic support which gives an excellent image, and in particular, film peeling, fog and spots of a silver halide photosensitive layer are prevented during development processing. The present invention relates to a photographic support that gives an image having good reproducibility of hue, gradation and the like without generation and excellent sharpness.

(Prior Art) Transparent plates and films such as TAC, PET, and polycarbonate, which are conventionally known as photographic supports, paper, synthetic paper, baryta paper, or a film containing a white pigment,
Compared with a plate or a metal plate such as an aluminum plate whose surface is anodized, a metal reflective or second
The use of a photographic support having a surface having a diffused reflection property provides a photographic or recording medium excellent in gradation reproducibility, hue reproducibility in color photography, and image sharpness. For example, JP-A-61-210346, Japanese Patent Application Nos. 61-168800 and 61-16880
No. 1, Dosho 61-168802, Dosho 61-168803, Dosho 61-1688
No. 04, Sho 61-168805, Sho 61-249873, etc.

Inorganic substances such as natural mica, fish scales and pearls can be used to give specular reflection or type 2 diffuse reflection, but most are metals such as aluminum, silver, gold, copper, chromium, nickel and platinum, or Aluminum is generally a good choice for the alloy. However, if a metal baser than silver is used for a support for a photographic or recording light-sensitive material using a silver halide photographic emulsion, fog or spots tend to occur during the development processing. For this reason, it is known to provide an adhesive layer of a thermoplastic resin. However, film peeling or the like is likely to occur during the development processing or during drying after the development, and there is a difficulty in providing a thin layer of, for example, 0.1 to 5 μm using a thermoplastic resin.

Also, due to long-term aging after development processing, a mirror surface or second
There is a risk that the seed diffuse reflectivity may deteriorate or reflectivity unevenness may occur.

(Object of the invention) An object of the present invention is to provide a photographic support that does not cause defects such as film peeling of the photosensitive material layer during or before and after the development processing, and the storability of the obtained image is improved. An object is to provide an excellent photographic support.

(Structure of the Invention) An object of the present invention is to provide a photographic support comprising an adhesive layer provided on a metal surface having specular reflectance or second-class diffuse reflectance, and vinylidene chloride, vinyl chloride, vinyl acetate and It was achieved by using 40-95% by weight of a copolymer containing maleic anhydride and 5-60% by weight of a polyurethaneurea resin.

The copolymer of vinylidene chloride, vinyl chloride, vinyl acetate and maleic anhydride according to the present invention is (a) 20 to 80 mol%.
Vinylidene chloride, (b) 20-80 mol% vinyl chloride,
A copolymer of (c) 5 to 20 mol% of vinyl acetate and (d) 0.1 to 5 mol% of maleic anhydride is preferable.

When the content of vinylidene chloride is 20% by weight or less, the hydrophobicity is lowered and the film strength of the adhesive layer when wet is weak, which is not preferable.
On the other hand, if the content of vinyl chloride is 20% by weight or less or 80% by weight or more, the solubility in organic solvents decreases, which is not preferable.

On the other hand, if the content of vinyl acetate is 20% by weight or more, blocking with the back surface of the support occurs, which is not preferable. Further, if it is 5% or less, coloring of the adhesive layer by the developer is not so preferable.

When the maleic anhydride content is less than 0.1% by weight, the adhesion to the silver halide emulsion layer and the strength are weakened, which is not preferable.

The polyurethane urea resin of the present invention has a urethane bond And urea bond Is a polymer having a large amount of in a molecular chain, and a resin obtained by reacting a polyvalent isocyanate or a prepolymer thereof with a polyvalent hydroxy compound or a polar liquid forming a continuous phase.

Examples of the polyvalent isocyanate or the polyvalent isocyanate prepolymer used in the present invention include, for example, m-
Phenylene diisocyanate, b-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diene Isocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-
Diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene- 1,2-diisocyanate, butylene-1,2-diisocyanate, ethylidyne diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-
Diisocyanates such as 1,4-diisocyanate, 4,4 ′,
Triisocyanates such as 4 ″ -triphenylmethane triisocyanate, toluene-2,4,6-triisocyanate, polymethylene polyphenylisocyanate,
Tetraisocyanate monomers such as 4'-dimethyldiphenylmethane, 2,2 ', 5,5'-tetraisocyanate or polyvalent isocyanates thereof are converted into polyvalent amines, polycarboxylic acids, polyvalent thiols, and polyvalent thiols. A compound added to a compound such as a hydroxy compound or an epoxy compound, in which two or more isocyanate groups remain in one molecule, may be mentioned.

Examples of polyhydric hydroxy compounds include aliphatic or aromatic polyhydric alcohols, hydroxypolyesters, hydroxypolyalkylene ethers, alkylene oxide adducts of polyamines, and the like. For example, catechol, resorcinol, hydroquinone, 1,2-dihydroxy-4-methylbenzene, 1,3-dihydroxy-
5-methylbenzene, 3,4-dihydroxy-1-methylbenzene, 3,5-dihydroxy-1-methylbenzene,
2,4-dihydroxyethylbenzene, 1,3-naphthalene diol, 1,5-naphthalene diol, 2,7-naphthalene diol, 2,3-naphthalene diol, o, o'-biphenol, p, p'-biphenol, 1 , 1'-Bi-2-naphthol, bisphenol A, 2,2'-bis- (4-hydroxyphenyl) butane, 2,2'-bis- (4-hydroxyphenyl) -isopentane, 1,1 ′ -Bis- (4-hydroxyphenyl) -cyclopentane, 1,1′-bis-
(4-Hydroxyphenyl) -cyclohexane, 2,2 '
-Bis- (4-hydroxy-3-methylphenyl) -propane, bis- (2-hydroxyphenyl) -methane,
Xylylene diol, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-heptanediol, 1,7-hepetanediol, 1,8-octanediol, 1,1,1-Trimethylolpropane, hexanetriol, pentanelithritol, glycerin and sorbitol, aromatic or aliphatic polyhydric alcohols and the like are used.

The hydroxypolyester used is, for example, one obtained from a polycarboxylic acid and a polyhydric alcohol.
Examples of the polycarboxylic acid for forming the hydroxypolyester include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, isophthalic acid, terephthalic acid, gluconic acid and the like. As the polyhydric alcohol, those described above are used.

Hydroxypolyalkylene ethers are, for example, the condensation products of alkylene oxides and polyhydric alcohols. As the alkylene oxide, butylene oxide or amylene oxide used for producing the hydroxypolyalkylene ether, the compounds described above are used as the polyhydric alcohol.

The alkylene oxide adduct of a polyvalent amine refers to a compound in which one or more hydrogen atoms in the amino group of the polyvalent amine are replaced with alkylene oxide. Examples of polyvalent amines for producing alkylene oxide adducts of polyvalent amines include aromatic polyvalent amines such as o-phenylenediamine, b-phenylenediamine, diaminonaphthalene, ethylenediamine, 1,3-propylenediamine And aliphatic polyamines such as diethylenetriamine and 1,6-hexamethylenediamine. Examples of alkylene oxide adducts include ethylene oxide, propylene oxide, butylene oxide and the like.

The most representative polar liquid forming the continuous phase is water, but its equivalent, for example, ethylene glycol,
Glycerin, butyl alcohol, octyl alcohol and the like are also used.

The ratio of vinylidene chloride, vinyl chloride, vinyl acetate, maleic anhydride copolymer and polyurethane urea resin is
The weight ratio is 95/5 to 40/60, preferably 90/10 to 50/50. When the proportion of the polyurethane urea resin is less than 5% by weight, the adhesion to the metal reflecting surface is insufficient, and when it is more than 60% by weight, the adhesion between the adhesive layer and the silver halide emulsion layer is insufficient.

It is effective to apply a pretreatment such as corona discharge, glow discharge, or flame treatment in order to strengthen the adhesion with the silver halide emulsion after the adhesive layer is applied and dried. An undercoat layer of gelatin may be provided before coating the silver halide emulsion.

The adhesive layer of the present invention is required to be in contact with the metal reflection layer on the surface of the support base material and be applied as an extremely thin and uniform coating of 0.1 to 10 μm. If the thickness is 0.1 μm or less, adhesion failure between the metal reflection layer and the silver halide photosensitive layer occurs, and if it is 10 μm or more, it is disadvantageous in terms of cost and reproducibility such as hue and gradation deteriorates.

Further, as the diluting solvent for the adhesive layer of the present invention, any of ketones such as MEK / acetone, chlorides such as tricrene, esters such as ethyl acetate / butyl acetate, and aromatic organic solvents such as triol can be used. Is particularly preferably ethyl acetate.

Further, the adhesive layer of the present invention is largely different in that it is provided on the upper surface of a metal thin layer having metal reflectivity or type 2 diffuse reflectivity, but it is not disclosed in JP-A-51-114120, JP-A-54-94025, and JP-A-4949. -11118
It can be applied using the method shown in No. Specifically, for example, a day coat method, an air knife coat method, a curtain coat method, a roller coat method, a doctor coat method, a wire bar coat method, a slide coat method, a gravure coat method, a reverse coat method or the like can be applied.

Supports having a specular or type II diffuse reflective surface according to the invention may be provided with a thin layer of material on the support substrate that provides the specular reflector when the surface is sufficiently smooth. . For example, JP-A-61-210346 and Japanese Patent Application No. 61-168800.
Nos. 61-168801 and 61-249872 are used. Preferably, the metal is F, a metal described in F. Benford et al., J. Opt. Soc. Amer, Vol. 32, pages 174-184 (1942), for example, silver, aluminum,
Gold, copper, chromium, nickel, platinum, and the like and alloys thereof, such as aluminum / magnesium and cinch yu. It is also possible to use a layer filled with the above-mentioned metal powder or a powder of natural mica or scale which gives an inorganic substance a specular reflection property.

The substrate of the support is conventionally used as a support,
For example, plastic films, papers, RC-papers, synthetic papers, metal plates, etc., and plates of polymers and copolymers such as polycarbonate, polystyrene, polyacrylate, polymethyacrylate, PET, etc., which have excellent dimensional stability. Particularly preferred is paper or RC-paper, which is obtained by laminating the pre-textured aluminum foil of the present invention by using low density polyethylene in combination with the polyethylene layer of RC-paper, and easily and at a low cost level. You can For use in a disk-like recording medium described in Japanese Patent Application No. 61-249873, polycarbonate, polystyrene, polyimide resin and ceramic materials which are particularly excellent in dimensional stability and physical strength are used.

The support of the present invention can be widely used as a photographic reflection support, and a silver halide emulsion layer for black and white photographic paper can be provided and a protective layer can be provided thereon. Similarly, a photosensitive material for color photographic paper can be prepared by providing two or more photosensitive silver halide emulsion layers each having a different spectral sensitivity for ordinary color photographic paper and containing different color couplers. Further, a color reflection light-sensitive material, a direct positive type color photographic paper, or a direct positive type color copy material using an optical fog method can be prepared. A red, green, and blue-sensitive silver halide emulsion layer containing silver halide grains having different spectral sensitivities and a dye used in a silver die breach (SDB) method is provided on the support. Provided
We can also make SDB type print photosensitive materials. or,
It can also be applied to reflective disc plates, disc films and recording materials using silver halide.
For more details, Japanese Patent Application Nos. 61-168802 and 61-168803,
61-168804, 61-168805 and 61-249873
It can be widely applied to the light-sensitive materials described in JP-A Nos. 61-259794 and 61-275572.

A mordant layer may be provided on the support according to the present invention to diffuse and transfer a color-developing dye to form a color image. It can also be used as a material for forming a silver diffusion transfer type silver image by providing a physical development nucleus in the undercoat layer on the support of the present invention. In addition, development inhibitory or desilvering inhibitory substances such as JP-B-59-3737 and JP-A-50-65230, for example, iodoodor ion, bromine ion, a heterocyclic compound having a mercapto group and iminosilver formation It is also possible to provide an adsorption layer ADL of possible heterocyclic compounds and the like.

Further, the photographic support of the present invention is disclosed in U.S. Pat.
6, JP-A-60-133449, 59-218443, JP-A-60-79
It can also be applied to a photothermographic material and / or a dye fixing material (image receiving material) described in JP-A No. 709.

(Advantages of the Invention) By providing the adhesive layer of the present invention on a metal surface having specular reflection or type II diffuse reflection, film peeling, fog, spots, etc. of the silver halide photosensitive layer can be prevented during development processing. An image that does not occur, has good reproducibility of hue and gradation, and has excellent sharpness can be obtained.

(Examples of the Invention) Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 6 Comparative Examples 1 to 4 As a substrate, 2% of silica having an average particle size of 3 μm was filled.
A 25 μm polyethylene terephthalate film was placed in a vacuum vapor deposition apparatus and vacuum vapor deposition was performed under a vacuum degree of 10 ⁻⁵ torr to form an aluminum vapor deposition film having a thickness of 600 Å on the surface of the substrate.

An adhesive layer having the composition shown in Table 1 was diluted with ethyl acetate, dried, and applied to the surface of the deposited film to a concentration of 5 g / m ² after drying.
Oven dried at 00 ° C. for 2 minutes.

Next, the wood pulp consisting of 20 parts of LBSP and 80 parts of LBKP was processed with a disc cliff eyer to produce Canadian Freeness 300C.
Beat to C and add 1.0 part of sodium stearate, 0.5 part of anionic polyacrylamide, 1.5 parts of aluminum sulfate, 0.5 part of polyamide polyamine epichlorohydrin, 0.5 part of alkyl ketene dimer, all in an absolute dry weight ratio to wood pulp. Weighed 160 g / m ² by paper machine
Paper was made.

The density was 1.0 g / cm ³ with a machine calender. After corona discharge treatment of this base paper, low density polyethylene (MI
= 7 g / 10 min, density 0.923 g / CC) was extruded and coated to form a polyethylene resin layer having a thickness of 30 μm. Next, after the other surface (back surface) of the substrate was subjected to corona discharge treatment, a high-density polyethylene (MI = 8 g / 10
Min., Density 0.950g / CC) by extrusion coating, thickness 3
A polyethylene resin layer having a thickness of 0 μm was formed to prepare a double-sided polyethylene laminated paper.

Next, a polyurethane two-component type adhesive of the following composition was applied on the back side of the above-mentioned aluminum vapor deposition film (the surface opposite to the vapor deposition surface) so that the adhesive would be 3 g / m ² after drying.
Dry for 2 minutes at ℃ The coated surface and the low-density polyethylene surface of the double-sided polyethylene laminated paper were combined, and thermocompression bonding was performed at 80 ° C. and a pressure of 20 kg / cm.

A silver halide emulsion was coated on the above-mentioned support according to Example 4 of Japanese Patent Application No. 168801/1986 to obtain a color photographic printing paper.

The silver halide emulsion (1) used in the present invention was prepared as follows.

(2 solutions) Sulfuric acid (1N) 24CC (3 solutions) The following silver halide solvent (1%) 3CC (Liquid 1) was heated to 56 ° C., and (2nd liquid) and (3rd liquid) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 30 minutes. After a further 10 minutes, (Sixth solution) and (Sixth solution) were simultaneously added for 20 minutes. Five minutes after the addition, the temperature was lowered and desilvering was performed. Monodisperse cube with water and dispersed gelatin added, pH adjusted to 6.2, average particle size 0.45 μm, coefficient of variation (standard deviation divided by average particle size: s / d) 0.08, silver bromide 70 mol% A silver chlorobromide emulsion was obtained. Sodium thiosulfate was added to this emulsion for optimum chemical sensitization.

Next, silver halide emulsions having different silver chloride contents (2)
(3) (4) was prepared in the same manner by changing the amounts of KBr and NaCl in the 4th and 6th solutions and the addition times of the 4th and 5th solutions as shown in Table 2.

Table 3 shows the average grain size, coefficient of variation, and halogen composition of the silver halide emulsions (1) to (4).

A color photographic material was obtained by stacking the first to seventh layers shown in Table 4 on each support.

First layer: The silver halide emulsion (4) was spectrally sensitized by adding 7.0 × 10 ^-4 mol of the blue-sensitive sensitizing dye (a) per Ag × 1 mol. Further, the yellow coupler (b) and the color increase stabilizer (e) were mixed and dissolved with the solvent (f), dispersed, and added in a predetermined amount. This was applied to form a first layer.

Third layer: The silver halide emulsion (3) was spectrally sensitized by adding 4.0 × 10 ^-4 mol of a green-sensitizing dye (b) per 1 mol of Ag × 1 mol. Further, the magenta coupler (h) and the color-increasing stabilizer (i) were mixed and dissolved in the solvent (j), dispersed and added in a predetermined amount. This was applied to form a third layer.

Fifth layer: The silver-sensitive emulsion (2) was spectrally sensitized by adding a red-sensitive sensitizing dye (c) in an amount of 1.0 × 10 ^-4 mol per mol of Ag × 1. Further cyan coupler (n) and color increasing stabilizer (o)
Was mixed and dissolved in the solvent (f) and dispersed, and a predetermined amount was added. This was applied to form a fifth layer.

A coating liquid was obtained in the same manner for the second layer, the fourth layer, the sixth layer, and the seventh layer.

The first layer, the second layer, the third layer, and the fourth layer were formed on the undercoat layer of the support by a conventional method so that the predetermined amounts shown in Table 4 were obtained.
Layers 5, 5 and 6 and the seventh layer were applied to obtain sample Nos. 1 to 6 and comparative sample. (See Table 5) The above sample was subjected to gradation exposure for sensitometry through a blue, green and red three-color analysis filter using a 2854 ° K light source or image exposure for printing by stretching it through a negative film.

Thereafter, a photographic image was obtained through the steps of color development, bleach-fixing and rinsing.

Current image Formulation A 35 ° C 45 seconds Bleach-fixing formulation A 35 ° C 45 seconds Rinse formulation A 28-35 ° C 1 minute 30 seconds Color developer A Water 800CC Diethylenetriaminepentaacetic acid 1.0g Sodium sulfite 0.2g N, N-diethylhydroxylamine 4.2 g Potassium bromide 0.6g Sodium chloride 1.5g Triethanolamine 8.0g Potassium carbonate 30g N-ethyl-N- (β-methanesulfonamidoethylamino) -3-methyl-4-aminoaniline sulfate 4.5g 4,4 ' -Diaminostilbene type fluorescent whitening agent (Whitex4, Sumitomo Chemical Co., Ltd.) 2.0g Water is added to 1000CC KOH to pH 10.25 Bleaching treatment Fixing solution formulation A Ammonium thiosulfate 150ml (54wt%) Na ₂ SO ₃ 15g NH ₄ [Fe (III) (EDTA)] 55g EDTA ・ 2Na 4g Glacial acetic acid 8.61g Total amount of water 1000ml (pH5.4) Rinse solution formulation A EDTA ・ 2Na ・ 2H ₂ O 0.4g Total amount of water 1000ml (PH 5.4) (M) Solvent (isoC ₉ H ₁₈ O ₃ P = O The photographic printing paper thus obtained was evaluated by the adhesion test method shown below.

Adhesion test method 1) Adhesion test before drying before processing Adhere polyester adhesive tape (Nitto Mylar tape No.31) on the emulsion surface after drying the photographic emulsion and peel it off momentarily.

2) Adhesion test during wet treatment In the wet condition, the emulsion surface of the sample after development, fixing, and water washing is scratched with a stylus with a stylus and rubbed 10 times with rubber applied with a load of 3 kg.

3) Adhesion test after processing and drying After developing, fixing, rinsing and drying, the emulsion surface of the sample is scratched in a stylus with an iron brush, and Nitto Mylar tape No. 31
After 24 hours at 25 ° C. and 55% RH, the tape is instantaneously peeled off.

In the tests of 1) to 3) above, those in which the emulsion layer did not peel at all were classified as Class A, those which peeled slightly were classified as Class B, and those that peeled off slightly were classified as Class C, but those with practically lower limit are Class C. Those that peel off to some extent are classified as D grade.

 The results of the adhesion test are shown in Table 5.

As is clear from the results in Table 5, it is clear that the adhesion of the silver halide emulsion layer is improved by providing the adhesion layer of the present invention.

Claims (1)

[Claims] 1. A photographic support comprising an adhesive layer provided on a metal surface having specular reflectivity or second class diffuse reflectivity, wherein the adhesive layer comprises (1) vinylidene chloride, vinyl chloride, vinyl acetate and maleic anhydride. Copolymer of 40-95% by weight (2)
A photographic support comprising 5 to 60% by weight of a polyurethane urea resin.